Process for manufacturing monohalogen derivatives of naphthostyril and substitution products thereof



Patented Sept. 13, I 1932 VIIEBNER znnwiiox, o moneaemjammrnnnxron'r-oiv-rnu mnm, GERMANY, AS-

srenon r0 GENERAL 'ANILINE 'w'o'nxs,"

OF DELAWARE INC-,9]? NEW YORK,

n. Y, A conronn'rro v N0 Drawing. Ap ncatib filed. April 5, 1928,seriarNo 267,810, and in German The subject matter of my invention is aprocess for manufacturing monohalogen de- Hal. I

wherein the Xs are hydrogen atoms of which 1 one or more may be replacedby a monovalent substituent. This process consists in acting onnaphthostyril and its nuclear substitution u-oducts in which thepara-position to the H-group is free with halogenating agents under suchconditions that monohalogenated compounds are produced chiefly orexclusively. A main condition for obtaining the desired result is theuse of haloge'nating'agents in amounts not considerablyabove thetheoretical quantity forintroduclng one halogen atom into the nucleus}.As hal'ogenating agents, free halogen or agents ogen, for instancesulfurylchloride or a chlorate in the presence of hydrochloric-acid, may

Advantageously one works in the be used.

dlluent of an morganic' presence of a suitable or organic character. Y

The uniform formation ofimonohalo'gen derivatives by my method issurprising, as it was not to be expected that the reaction could bestopped after theformation of the monohalogen derivative, sincenaphthalene compounds and especially naphthostyril are disposed to yielddihalogen-derivatives.

The monohalogenated naphthostyril compounds could be prepared hitherto,only 1n a;

complicated manner, 1. e.by nitrating naphthostyril, reducing thenitro-body, thus formed, and converting the amino compound according toSandmeyersreaction into the corresponding halogen-derivative. By myprocess they are produced in a simple manner with an excellent yield andin a very pure state. They are important intermediates'for theproduction of dyestuffs and pharmaceutical products.

delivering ha l with heating, in

chl'oric acid, then the solution is cooled down,

VANDY-SUBSTITUTION rnonuc'rs THEREOF April 9, 1927.

In order to further illustrate my invention the following examples aregiven, the parts being by weight and all temperatures in Centigradedegrees; 0

nor to theexact conditions Example 1 169 parts of naphthostyril(obtainable for instance according to U. S. Patent No. 1,646,-

are dissolved in 2200 parts of concentrated sulfuric acid and mixed with3 parts of iodine. q Then chlorine is slowly passed through the solutionat about 1520 unti1 a.

product has a test'shows that the reaction melting; point of about 260;The mass is poured" on ice and the precipitated l-chloronaphthostyril isfiltered o'fiI'. When'crystaL' it represents lized from glacial aceticacid,

as stated by yellow needles melting at 270 Eckstrand and correspondsprobably to the formula:- I v o( 1-NH Y E mample 2 I 169 parts ofnaphthost'yril are dissolved,

7000 parts of crude hydrowhereby the hydrochloric salt of thenaphthostyril separates. aqueous solution of 40 rate is allowed to runslowly,

parts of sodium chlowhile stirring,

the temperature being advantageously kept at 1520. After stirring forsome time, the residue is filtered ioif, washed and dried. Thechloronaphthostyril, thus obtained in a nearly theoretical yield, isidentical with the compound produced according to Example 1.

n Ewample I 15 parts of sulfurylrchloride are slowly introduced at 50-60 into a solution of 17 parts ofnaphth'o'styril in 27 0 parts oftetrachloro but I wish it to be under-- stood'that my invention is notlimited to the examples given, stated therein.

Into this suspension an ethane: The temperature increases and'the formedchloronaphthostyril is precipitated as yellow needles. After keeping thetemperature at 60 for some time, the mass is cooled and the reactionproduct is filtered off and dried. In this manner the same product isobtained as described in the foregoing examples, melting Without anypurifis cation at 265.

Instead of totrachloroethane other suitable dissolving or suspendingagents may be used as glacial acetic acid, nitrobenzene,trichlorobenzene.

Eocample 1,. 10 parts of 5-ethoXy-naphthostyril, ob tainable, forexample, according to U. S.

Patent No. 1,779,314, are dissolved in 200 parts of glacial acetic acid.A small quantity of iodine is added and 8 parts of sulfurylchloride areintroduced at 50-60.

' The resulting l-chloro-5-ethoXy-naphthostyof iodine are added and 'iis obtained ril corresponding probably to the-formula:

0ONH

02H. 1 separates from the hot solution as light yellowcompact needles.When cold it is filtered off, washed with glacial acetic acid and water,and dried. It may be purified by dissolving it in hot glacial aceticacid and precipitating it therefrom by means of water. It melts at about250-252".

Example 5 and is identical with the bromonaphthostyril prepared byEckstrand in a complicated manner (Journal fur praktische Chemie (2)vol. 38,-page 173).

Instead of tetrachloroethane other suitable idissolving or suspendingagents may be usedv such as glacial acetic acid, nitrobenzene,trichlorobenzene etc.

In the same manner the nuclear substitution products of naphthostyrilyield. nuclear substituted mono'-bromonaphthostyrils.

I claim: r

1. A process for manufacturing monohalo-- gen derivatives ofnaphthostyril compounds,

corresponding probably to the general formula:

OCNH

l I X Hal.

wherein the Xsmean hydrogen atoms of which one may be replaced by analkoxy group, which process comprises treating a naphthostyrilcompoundin which the paraposition to the iminogroup is free with anuclear halogenating agent in amounts not considerably abovethetheoretical quantity for introducing one halogen atom into thenucleus.

2. A process for manufacturing monochloro derivatives of naphthostyrilcompounds corresponding probably to the general formula: 1

wherein the Xs mean hydrogen atoms of which one may berreplaced by analkoXy group, which process comprises treating a naphthostyril compoundin which the para position to the imino-group is free with a nuclearchlorinating agent in amounts not considerably above the theroreticalquantity for introducing one chlorine atom into the nucleus. I

3. As a new product the 4-chloro-5-etl1- oXyna'pht-hostyrilcorresponding probably to the formula o=oN-H which product representslight yellow compact needles melting at about 250252, soluble in organicsolvents, insoluble in water.

In testimony whereof, I aflix my signature.

' .WERNER ZERWEGK.

